TW201839029A - High molecular weight compound having substituted triarylamine skeleton - Google Patents

Abstract

A high molecular weight compound of the present invention includes a substituted triarylamine structural unit represented by a General Formula (1) below: (1) wherein Ar1 and Ar2 each is a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group; R1 and R2 each represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkyloxy group or a cycloalkyloxy group; and X, Y and Z each is an aryl group, a heteroaryl group or any of the same groups as those represented by the aforementioned R1 and R2 provided that at least one of X, Y and Z is the aryl group or the heteroaryl group.

Description

High molecular weight compound with substituted triarylamine skeleton

The present invention relates to an ideal high-molecular-weight compound suitable for a variety of display devices, which is an organic electroluminescent device that is a self-luminous device, and the device.

Since the organic EL element is a self-luminous element, it is brighter and has better visibility than a liquid crystal element, and it can provide a clear display. So some people have actively researched.

The organic EL element has a structure in which a thin film (organic layer) of an organic compound is sandwiched between an anode and a cathode. The method of forming a thin film can be roughly classified into a vacuum evaporation method and a coating method. The vacuum evaporation method is a method in which a low molecular weight material is mainly used to form a thin film on a substrate in a vacuum, and it is a practical technology. On the other hand, the coating method is a method that mainly uses high molecular weight materials to form a thin film on a substrate by using a solution such as inkjet and printing. The material is highly efficient and suitable for large areas and high definition. Indispensable technology for area organic EL displays.

The vacuum vapor deposition method using a low-molecular-weight material has extremely low use efficiency of the material. If the size is increased, the deflection of the mask will increase, making it difficult to uniformly vapor-deposit a large substrate. There is also a problem that the manufacturing cost also increases.

On the other hand, polymer materials can be coated with a solution obtained by dissolving them in an organic solvent. Even large substrates can form a uniform film, and coatings such as inkjet and printing methods can be used for this. law. Therefore, the use efficiency of materials can be improved, and the manufacturing cost of component manufacturing can be greatly reduced.

There have been various studies on organic EL devices using polymer materials so far, but there are still problems in which device characteristics such as luminous efficiency and lifetime are not necessarily satisfactory (see, for example, Patent Documents 1 to 5).

Also, a typical hole transporting material used in high-molecular organic EL devices has hitherto been known as a fluorene polymer called TFB (see Patent Documents 6 to 7). However, TFB has insufficient hole-transporting properties and insufficient electron-blocking properties. Therefore, a part of the electrons directly passes through the light-emitting layer, and a problem of better light-emitting efficiency cannot be expected. Moreover, since the adhesiveness with the film of an adjacent layer is low, there exists a problem that the life of an element cannot be expected to be long. [Prior Art Literature] [Patent Literature]

[Patent Document 1] JP 2005-272834 [Patent Document 2] JP 2007-119763 [Patent Document 3] JP 2007-162009 [Patent Document 4] JP 2007-177225 [Patent Document 5] International Publication WO2005 / 049546 [Patent Document 6] Japanese Patent No. 4375820 [Patent Document 7] International Publication WO2005 / 059951

[Problems to be Solved by the Invention] An object of the present invention is to provide a high-molecular material having excellent hole injection and transportation performance, an electron blocking ability, and high stability in a thin film state. Another object of the present invention is to provide an organic EL device having an organic layer (thin film) formed of the above-mentioned polymer material, and having high luminous efficiency and long life. [Solution to the problem]

The inventors of the present case waited to see that the substituted triarylamine structure had high hole injection and transport capabilities. A variety of high molecular weight compounds with substituted triarylamine structures were synthesized and discussed. As a result, it was found that in addition to hole injection and transport capabilities, high molecular weight compounds with novel structures that are more heat resistant and thin film stable, have completed the present invention.

According to the present invention, there is provided a high molecular weight compound including a substituted triarylamine structural unit represented by the following general formula (1). [Chemical 1] In the formula, Ar ¹ and Ar ^{2 are} each a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group, and R ¹ and R ^{2 are} each a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, or a carbon atom. Alkyl groups of 1 to 8, cycloalkyls of 5 to 10 carbons, alkenyls of 2 to 6 carbons, alkoxys of 1 to 6 carbons, or cycloalkoxys of 5 to 10 carbons, X , Y, and Z, provided that at least one of them is an aryl group or a heteroaryl group, and represents an aryl group, a heteroaryl group, or the same group as the group represented by the aforementioned R ¹ and R ² .

Among the high molecular weight compounds of the present invention, the following aspects are preferred. (1) Containing the aforementioned structural unit as a repeating unit and having a weight average molecular weight of 10,000 or more and less than 1,000,000 in terms of polystyrene. (2) In the above general formula (1), X and Y are aryl or heteroaryl, preferably these groups have no substituents, and more preferably these groups are phenyl, biphenyl, bitriphenyl, Naphthyl, phenanthryl, fluorenyl, naphthylphenyl or triphenylenyl. (3) In the general formula (1), R ¹ , R ² and Z are a hydrogen atom or a deuterium atom. (4) In the aforementioned general formula (1), X and Z are aryl or heteroaryl groups, preferably these groups have no substituents, and more preferably these groups are phenyl, biphenyl, and bitriphenyl , Naphthyl, phenanthryl, fluorenyl, naphthylphenyl, or triphenylene. (5) In the general formula (1), R ¹ , R ² and Y are a hydrogen atom or a deuterium atom. (6) In the foregoing general formula (1), X, Y and Z are all aryl or heteroaryl groups, preferably these groups have no substituents, and more preferably these groups are phenyl, biphenyl, and biphenyl Triphenyl, naphthyl, phenanthryl, fluorenyl, naphthylphenyl or triphenylene. (7) In the general formula (1), R ¹ and R ² are a hydrogen atom or a deuterium atom. (8) In addition to the unit represented by the aforementioned general formula (1), it has a structural unit having a group having at least one aromatic hydrocarbon ring or a triarylamine skeleton.

According to the present invention, there is provided an organic EL element having a pair of electrodes and at least one organic layer sandwiched between the electrodes, characterized in that the organic layer contains the above-mentioned high molecular weight compound.

In the organic EL device of the present invention, the organic layer is preferably a hole transporting layer, an electron blocking layer, a hole injection layer or a light emitting layer. [Effect of the invention]

The above-mentioned high molecular weight compound of the present invention having the substituted triarylamine structural unit (divalent base) represented by the general formula (1), for example, is a polymer having the structural unit as a repeating unit, preferably GPC ( The weight average molecular weight measured by gel permeation chromatography) in terms of polystyrene falls in the range of more than 10,000 and less than 1,000,000. The high molecular weight compound has the following characteristics: (1) good hole injection characteristics, (2) large hole mobility, (3) excellent electron blocking ability, (4) stable film state, (5) excellent heat resistance . An organic layer made of such a high molecular weight compound, such as an organic hole transport layer, an electron blocking layer, a hole injection layer, or a light emitting layer, is formed between a pair of electrodes, and has the following advantages: (1) Luminous efficiency and High power efficiency, (2) low practical driving voltage, and (3) long life.

<Substituted triarylamine structural unit> The substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention is a divalent group and is represented by the following general formula (1). [Chemical 2]

In the general formula (1), Ar ¹ and Ar ^{2 are} each a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group, and Ar ¹ and Ar ² may be mutually the same group. The aromatic ring possessed by the divalent aromatic hydrocarbon group may be a monocyclic ring or a condensed ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, an indene ring, a fluorene ring, a fluorene ring, and a fluoran ring. These aromatic rings may have a substituent. The heterocyclic ring possessed by the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of such a heterocyclic ring include a pyridine ring, a pyrimidine ring, and a tricyclic ring. Ring, quinoline ring, isoquinoline ring, benzofuran ring, benzothiophene ring, indole ring, carbazole ring, benzo Azole ring, benzothiazole ring, dibenzofuran ring, quinine Phenoline ring, benzimidazole ring, pyrazoline ring, dibenzofuran ring, dibenzothiophene ring, Pyrimidine ring, morpholine ring, acridine ring, carboline ring and the like. These aromatic heterocyclic rings may have a substituent.

The above-mentioned aromatic ring and aromatic heterocyclic ring may have substituents other than a deuterium atom, a cyano group, a nitro group, and the like, as well as the following groups. Halogen atom, for example: fluorine atom, chlorine atom, bromine atom, iodine atom; alkyl group, especially those having 1 to 8 carbon atoms, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl Base, third butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, n-heptyl, isoheptyl, octyl heptyl, n-octyl, isooctyl, neooctyl Alkoxy, especially those with 1 to 8 carbons, for example: methoxy, ethoxy, propoxy; alkenyl, for example: vinyl, allyl; aryloxy, for example: phenoxy, tolueneoxy Aryl; for example: phenyl, biphenyl, bitriphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, fluorenyl, fluorenyl, allenylfluorenyl, triphenylene ; Heteroaryl, such as: pyridyl, pyrimidinyl, tris Base, thienyl, furyl, pyrrolyl, quinolinyl, isoquinolinyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzo Oxazolyl, benzothiazolyl, quinine Phenyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, carbolinyl; arylvinyl, for example: styryl, naphthylvinyl; fluorenyl, for example: ethyl Fluorenyl, benzamidine;

These substituents may further have the substituents exemplified above. Furthermore, it is preferred that these substituents exist independently of each other, but these substituents may be bonded to each other through a single bond, or may have a methylene group, an oxygen atom, or a sulfur atom of a substituent to form a ring. .

In the present invention, the Ar ¹ and Ar ^{2 are} preferably a carbazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a naphthyl group, a phenanthryl group, a phenyl group, and a substituted fluorenyl group. The substituents possessed by the fluorenyl group are preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and phenyl.

In the aforementioned general formula (1), R ¹ and R ² may be mutually the same, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group or an alkoxy group having 1 to 6 carbon atoms. , A cycloalkyl or cycloalkoxy group having 5 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryloxy group.

Examples of the alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, alkenyl group, and aryloxy group in the R ¹ and R ² include the following groups. Alkyl (C ₁ ~ C ₆ ), for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, n-pentyl, isopentyl, neopentyl , N-hexyl, etc .; alkoxy (C ₁ ~ C ₆ ), for example: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, third butoxy, n-pentyloxy Group, n-hexyloxy, etc .; Cycloalkyl (C ₅ ~ C ₁₀ ), for example: cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, etc .; cycloalkoxy (C ₅ ~ C ₁₀ ), For example: cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, 1-adamantyloxy, 2-adamantyloxy, etc .; alkenyl (C ₂ ~ C ₆ ), such as : Vinyl, allyl, isopropenyl, 2-butenyl, etc .; aryloxy, such as phenoxy, tolyloxy, etc.

The groups R ¹ and R ² may have a substituent. These substituents are the same as the substituents that the divalent groups Ar ¹ and Ar ² may have, and the point that these substituents may further have substituents is the same as the substituents that Ar ¹ and Ar ² may also have. . In addition, the above-mentioned R ¹ , R ² , and various substituents preferably exist independently of each other, but, like the substituents that Ar ¹ and Ar ² may also have, they may be bonded to each other to form a ring.

Among the high molecular weight compounds of the present invention, the aforementioned R ¹ and R ^{2 are} preferably a hydrogen atom and a deuterium atom. In terms of synthesis, a hydrogen atom is most preferred.

In the general formula (1), X, Y, and Z may be the same as each other. The condition is that at least one of X to Z is an aryl group or a heteroaryl group, and is an aryl group, a heteroaryl group, or R. ¹ and R ² represent the same group.

Examples of the groups represented by R ¹ and R ^{2 are} as described above, but examples of the aryl group and the heteroaryl group include the following examples. Examples of aryl (monovalent aromatic hydrocarbon group); phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, fluorenyl, fluorenyl, allenylfluorenyl and the like. Examples of heteroaryl groups (monovalent aromatic heterocyclic groups); pyridyl, pyrimidinyl, tris Base, furyl, pyrrolyl, thienyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, benzo Oxazolyl, benzothiazolyl, quinine Phosphono, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, Pyridyl, morpholinyl, acridinyl, carbolinyl and the like.

The aryl group and the heteroaryl group may have a substituent. These substituents are the same as the substituents that the divalent groups Ar ¹ and Ar ² may have, and these substituents may further have a substituent, and are also substituted with Ar ¹ and Ar ² The same. For example, the aryl group and the heteroaryl group may have a phenyl group as a substituent, and the phenyl group may further have a phenyl group as a substituent. That is, if an aryl group is taken as an example, the aryl group may be biphenyl, bitriphenyl, or triphenylene.

In addition, the above-mentioned aryl group, heteroaryl group, and various substituents preferably exist independently of each other, but may also be bonded to each other to form a ring, as may the substituents that Ar ¹ and Ar ² may have.

In the present invention, the combinations of the bases shown by X to Z have the following patterns (a) to (c). Pattern (a); a pattern in which X and Y are an aryl group or a heteroaryl group and Z is another group (the same groups as those represented by R ¹ and R ² ). Pattern (b); a pattern in which X and Z are an aryl group or a heteroaryl group and Y is another group (the same groups as those represented by R ¹ and R ² ). Pattern (c); X, Y and Z are patterns of aryl or heteroaryl.

In the above-mentioned form, it is preferable that the aryl group and the heteroaryl group have no substituent, and more preferably phenyl, biphenyl, bitriphenyl, naphthyl, phenanthryl, fluorenyl, naphthylphenyl or triphenylene. In the above-mentioned patterns (a) and (b), Z or Y which is a group other than an aryl group and a heteroaryl group is preferably a hydrogen atom or a deuterium atom.

In the present invention, specific examples of the substituted triarylamine structural unit represented by the general formula (1) are shown as structural units 1 to 135 in FIGS. 1 to 45. In the chemical formulas shown in FIG. 1 to FIG. 45, the dashed line represents a bonding hand to an adjacent structural unit, and the front end extending from the ring is a free solid line. Unlike the general formula (1), it represents its The free front end is methyl.

<High-molecular-weight compound> The high-molecular-weight compound of the present invention having the structural unit represented by the general formula (1) described above has the hole injection characteristics, hole mobility, electron blocking ability, film stability, heat resistance, etc. The characteristics are excellent, but from the viewpoint of making these characteristics higher and ensuring film-forming properties, it is preferable to use a polymer having the above-mentioned structural unit as a repeating unit. For example, the weight-average molecular weight in terms of polystyrene measured by GPC is 10,000 or more and less than 1,000,000, more preferably 10,000 or more and less than 500,000, and more preferably 10,000 or more and less than 200,000.

In addition, the high molecular weight compound of the present invention may be a homopolymer having the above-mentioned structural unit. For example, in order to ensure the applicability when forming an organic layer in an organic EL element by coating, the adhesion with other layers, Durability, preferably a copolymer with other structural units. Such other structural units include, for example, a structural unit for improving solubility in an organic solvent, and a structural unit for improving thermal crosslinkability of a polymer.

The structural unit for improving the solubility in an organic solvent has at least one aromatic hydrocarbon ring, and specific examples thereof are shown in formulas (2a) to (2x) in FIGS. 46 to 50.

In the above formulas (2a) to (2x), the dashed line represents the solid line extending from the ring to the bonding hand of the adjacent structural unit, and the front end is a methyl group. In the above formula, a to d are the following numbers. a = 0, 1, or 2 b = 0, 1, 2, or 3 c = 0, 1, 2, 3, or 4 d = 0, 1, 2, 3, 4 or 5

In formulas (2a) to (2x), R represents a hydrogen atom, a deuterium atom, a cyano group, or a nitro group; a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; each has a carbon number of 40 or less (especially 3 ~ 40) alkyl, cycloalkyl, alkoxy or thioalkoxy. In addition, Ar ⁵ to Ar ⁸ may be the same as or different from each other, and represent a monovalent or divalent aromatic hydrocarbon group or aromatic heterocyclic group. Examples of the monovalent aromatic hydrocarbon group or aromatic heterocyclic group include the same groups as those exemplified as the aryl group or the heteroaryl group with respect to the groups X to Z of the general formula (1). The divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group are the same as those exemplified for the groups Ar ¹ and Ar ² in the general formula (1). Of course, these groups may also have substituents.

In addition, in order to improve the thermal crosslinkable structural unit, the structural unit having a triarylamine skeleton is different from the structural unit represented by the general formula (1), and specific examples thereof are shown in formulas (3a) to (3y) ). In this equation, the dashed line, R, and a to d all have the same meaning as those in the aforementioned equations (2a) to (2x).

In the high molecular weight compound of the present invention, when the structural unit 1 represented by the general formula (1) is represented by A, the structural unit having better solubility in an organic solvent is represented by B, and the structural unit in order to improve thermal crosslinkability is When C is expressed, the content of the structural unit A is 1 mol% or more, and more preferably 5 mol% or more. The content of the structural unit A is included as a condition, and the content of the structural unit B is 1 mol% or more. In particular, the amount of 30 to 90 mol%, and further containing the structural unit C of 1 mol% or more, especially 5 to 20 mol%, if it contains structural units A, B and C in accordance with such conditions A terpolymer is most suitable for forming an organic layer of an organic EL device.

Such a high molecular weight compound of the present invention can be synthesized through the Suzuki polymerization reaction and HARTWIG-BUCHWALD polymerization reaction to form a C-C bond or a C-N bond, respectively, to link each structural unit. That is, a unit compound having each structural unit is prepared, and the unit compound is appropriately borated or halogenated, and a polycondensation reaction is performed using an appropriate catalyst to synthesize the high molecular weight compound of the present invention.

For example, a compound for introducing a structural unit of the general formula (1) may use a triarylamine derivative represented by the following general formula (1a). [Chemical 3] In the above formula, Q is a hydrogen atom or a halogen atom (especially Br), and Ar ¹ , Ar ² , X, Y, Z, and R ¹ and R ² are the same as those represented by the general formula (1).

That is, in the above general formula (1a), Q is a unit compound for introducing a structural unit of general formula (1) when Q is a hydrogen atom, and Q is a halogen compound for synthesizing a polymer when Q is a halogen atom.

The high molecular weight compound of the present invention is dissolved in aromatic organic solvents such as benzene, toluene, xylene, and anisole to prepare a coating liquid, and the coating liquid is coated on a predetermined substrate and dried by heating. , Can form thin films with excellent hole injection properties, hole transport properties, and electron blocking properties. This film also has good heat resistance, and further has good adhesion with other layers. For example, the above-mentioned high molecular weight compound can be used as a constituent material of a hole injection layer and / or a hole transport layer of an organic EL element. The hole injection layer or hole transport layer formed by using such a high molecular weight compound has higher hole injection, larger mobility, and higher electron blocking than those formed from conventional materials, and can be confined to light. Excitons generated in the layer can further increase the probability of recombination of holes and electrons, obtain high luminous efficiency, and reduce the driving voltage, thereby achieving the advantage of improving the durability of the organic EL element. It is needless to say that the high molecular weight compound of the present invention having the above-mentioned electrical characteristics is also suitably used for an electron blocking layer and a light emitting layer.

<Organic EL Element> An organic EL element including an organic layer formed using the high-molecular-weight compound of the present invention has a structure shown in FIG. 57, for example. That is, on the glass substrate 1 (which may be a transparent substrate such as a transparent resin substrate), a transparent anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7 are provided. Of course, the organic EL element to which the high molecular weight compound of the present invention is applied is not limited to the above-mentioned layer structure. A hole blocking layer may be provided between the light emitting layer 5 and the electron transporting layer 6, and the hole transporting layer 4 and An electron blocking layer or the like is provided between the light emitting layers 5, and an electron injection layer may be provided between the cathode 7 and the electron transporting layer 6. Furthermore, some layers may be omitted. For example, a simple layer structure including an anode 2, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6 and a cathode 7 on the substrate 1 may be provided. Moreover, it may be a two-layer structure in which layers having the same function are overlapped.

The high molecular weight compound of the present invention exhibits characteristics such as hole injectability and hole transportability, and is suitable as an organic layer (for example, hole injection layer 3, hole transport layer 4) provided between the anode 2 and the cathode 7 described above. , Light emitting layer 5 or a hole blocking layer (not shown).

In the above organic EL element, the transparent anode 2 may be formed of an electrode material known in itself, or may be formed by depositing an electrode material having a large work function such as ITO or gold on the substrate 1 (transparent substrate such as a glass substrate).

The hole injection layer 3 provided on the transparent anode 2 can be formed using a coating solution obtained by dissolving the high molecular weight compound of the present invention in an aromatic organic solvent such as toluene, xylene, or anisole. That is, by applying the coating solution to the transparent anode 2 by spin coating, inkjet, or the like, the hole injection layer 3 can be formed.

Moreover, instead of using the high molecular weight compound of this invention, you may form using the conventionally well-known materials, for example, the following materials. Porphyrin compounds typified by copper phthalocyanine; triphenylamine derivatives of the radiant type; aromatic amines having a structure bonded by a single bond or by a divalent group containing no heteroatoms (for example: triphenylamine terpolymers and tetramers) Materials); such as hexacyanatoazatriphenylene acceptor heterocyclic compounds; coated polymer materials, such as poly (3,4-ethylenedioxythiophene) (PEDOT), poly (styrene Sulfonate) (PSS) and the like. When a layer (thin film) is formed using such a material, a film can be formed by coating by a vapor deposition method, a spin coating method, an inkjet method, or the like. These methods are the same for other layers, and can be formed by a vapor deposition method or a coating method according to the type of the film forming material.

Similarly to the hole injection layer 3, the hole transport layer 4 provided on the hole injection layer 3 can be formed by using the high molecular weight compound of the present invention for spin coating, inkjet, or the like.

The hole transporting layer 4 may be formed using a well-known hole transporting material. Representatives of such hole transport materials are as follows. Benzidine derivatives, for example: N, N'-diphenyl-N, N'-bis (m-tolyl) benzidine (hereinafter referred to as TPD), N, N'-diphenyl-N, N'- Bis (α-naphthyl) benzidine (hereinafter referred to as NPD), N, N, N ', N'-Tetraphenylbenzidine; Amine derivatives, such as: 1,1-bis [4- (di- 4-Tolylamino) phenyl] cyclohexane (hereinafter referred to as TAPC); various triphenylamine terpolymers and tetramers; coated polymer materials that can also be used as hole injection layers.

The compound of the above hole transporting layer contains the high molecular weight compound of the present invention, and may be formed into a film individually, or two or more kinds may be mixed and formed into a film. Furthermore, one or more of the above compounds can be used to form a plurality of layers, and a multilayer film formed by such lamination can be used as a hole transporting layer.

Furthermore, it can be made into a layer that serves as both the hole injection layer 3 and the hole transport layer 4. Such a hole injection / transport layer can be formed by coating with a polymer material such as PEDOT.

In the hole transporting layer 4 (also the same as the hole injection layer 3), the materials commonly used for this layer can be further doped with p-bromoaniline hexachloroantimony and axene derivatives (for example, refer to WO2014 / 009310) Miscellaneous. The hole transporting layer 4 (or hole injection layer 3) can be formed using a high molecular weight compound such as a basic skeleton of TPD.

In addition, for an electron blocking layer (not shown) (which may be provided between the hole transporting layer 4 and the light emitting layer 5), a known electron blocking compound having an electron blocking effect may be used, such as a carbazole derivative, Compounds such as phenylsilyl and having a triarylamine structure are formed. Specific examples of the carbazole derivative and the compound having a triarylamine structure are as follows. Examples of carbazole derivatives 4,4 ', 4' '-tris (N-carbazolyl) triphenylamine (hereinafter referred to as TCTA), 9,9-bis [4- (carbazole-9-yl) benzene Yl) pyrene, 1,3-bis (carbazole-9-yl) benzene (hereinafter referred to as mCP), 2,2-bis (4-carbazole-9-ylphenyl) adamantane (hereinafter referred to as Ad-Cz) Example of a compound having a triarylamine structure 9- [4- (carbazole-9-yl) phenyl] -9- [4- (triphenylsilyl) phenyl] -9H-fluorene;

The electron blocking layer can be formed by using one or more of the known electron blocking materials alone, but it is also possible to form a plurality of layers using one or more of these electron blocking materials, and to form such a laminated layer The multilayer film serves as an electron blocking layer.

As the light-emitting layer 5 of the organic EL device, in addition to metal complexes of quinolinol derivatives mainly composed of Alq ₃ , complexes of various metals such as zinc, beryllium, and aluminum, anthracene derivatives, and Styrylbenzene derivatives, hydrazone derivatives, It is formed by a light emitting material such as an azole derivative or a polyparaphenylene vinylene derivative.

The light emitting layer 5 may be composed of a host material and a dopant material. As the host material in this case, in addition to the above-mentioned light-emitting material, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or the like can be used, and the high-molecular-weight compound of the present invention can also be used. As the dopant material, quinacridone, coumarin, rubrene, fluorene and their derivatives, benzopiperan derivatives, rhodamine derivatives, aminostyryl derivatives, and the like can be used.

Such a light-emitting layer 5 may have a single-layer structure using one or two or more types of each light-emitting material, or may have a multilayer structure in which a large number of layers are laminated.

Moreover, as for the light emitting material, a phosphorescent light emitting material can be used to form the light emitting layer 5. As the phosphorescent light-emitting material, a phosphorescent light-emitting body of a metal complex such as iridium or platinum can be used. For example: green phosphorescent emitters such as Ir (ppy) ₃ , blue phosphorescent emitters such as FIrpic, FIr ₆ , red phosphorescent emitters such as Btp ₂ Ir (acac), etc. These phosphorescent materials can be doped in electricity Used for hole injection / transportation host materials and electron transportability host materials.

As the host material for hole injection and transportability, carbazole derivatives such as 4,4'-bis (N-carbazolyl) biphenyl (hereinafter referred to as CBP), TCTA, and mCP can be used. High molecular weight compounds. In addition, as the host material for electron transportability, p-bis (triphenylsilyl) benzene (hereinafter referred to as UGH2), 2,2 ', 2' '-(1,3,5-phenylene) -reference (1 -Phenyl-1H-benzimidazole) (hereinafter abbreviated as TPBI) and the like.

The doping of the phosphorescent light-emitting material to the host material is preferably in the range of 1-30% by weight for the entire light-emitting layer in order to avoid concentration extinction. It is better to dope by co-evaporation.

As the light-emitting material, materials that emit delayed fluorescence, such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, can be used (see Appl. Phys. Let., 98, 083302 (2011)).

The high-molecular-weight compound of the present invention forms a light-emitting layer 5 by supporting a fluorescent emitter, a phosphorescent emitter, or a material that emits delayed fluorescence, called a dopant, and can reduce the driving voltage to achieve an organic EL with improved luminous efficiency element.

As a hole blocking layer (not shown) provided between the light emitting layer 5 and the electron transporting layer 6, a compound having a hole blocking effect known in itself can be used for formation. Examples of such well-known compounds having hole blocking effects include the following. Bactrinol derivatives such as Bathocuproin (hereinafter referred to as BCP); quinolinephenols such as bis (2-methyl-8-quinolinol) -4-phenylaluminum (III) (hereinafter referred to as BAlq) Derivative metal complexes; various rare earth complexes; triazole derivatives; three derivative; Diazole derivatives. These materials can also be used in the formation of the electron transport layer 6 described below, and can also be used as such a hole blocking layer and the electron transport layer 6.

Such a hole blocking layer may also have a single-layer or multi-layer laminated structure, and each layer may form one or two or more kinds of the compound having the above-mentioned hole blocking effect and the high molecular weight compound of the present invention.

The electron transporting layer 6 may use the naphthotriazole derivative of the present invention. In addition, a compound known per se as an electron transporting property may be used, for example, a metal complex of a quinoline phenol derivative mainly composed of Alq ₃ and BAlq. In addition, various metal complexes, triazole derivatives, derivative, Diazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinine A phthaloline derivative, a phenoline derivative, a silo derivative, and the like are formed. This electron transporting layer 6 can also be made into a single-layer or multi-layer laminated structure. Each layer can be formed using one type or two or more types of the aforementioned electron-transporting compounds.

In addition, if necessary, an electron injection layer (not shown in the figure) may be provided, which may be known per se, for example, alkali metal salts such as lithium fluoride and cesium fluoride, alkaline earth metal salts such as magnesium fluoride, and metals such as alumina An oxide or the like is formed.

For the cathode 7 of the organic EL element, an electrode material with a low work function such as aluminum, such as a magnesium-silver alloy, a magnesium-indium alloy, or an aluminum-magnesium alloy with a lower work function can be used as the electrode material.

In the present invention, the hole injection layer 3, the hole transport layer 4, the light emitting layer 5, and the unillustrated ones are formed by using a high molecular weight compound having a substituted triarylamine structure represented by the aforementioned general formula (1). At least any one of the electron blocking layers can achieve an organic EL element having high light-emitting efficiency and power efficiency, low practical driving voltage, low light-emitting start voltage, and excellent durability. In particular, this organic EL element has high luminous efficiency, reduced driving voltage, improved current resistance, and improved maximum luminous brightness. [Example]

Hereinafter, the present invention will be described based on experimental examples. In the following description, the structural unit represented by the general formula (1) possessed by the high-molecular-weight compound of the present invention is shown as "structural unit A", and the structural unit introduced to improve solubility in organic solvents is shown as "structural unit B" "The structural unit introduced to improve thermal crosslinkability is shown as" structural unit C ". The purification of the synthesized compound is carried out by a crystallization method using column chromatography and a solvent. Compound identification was performed by NMR analysis.

In order to produce the high molecular weight compound of the present invention, the following intermediates 1 to 41 were synthesized.

<Synthesis of Intermediate 1> [Chemical Formula 4] (Intermediate 1) Intermediate 1 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. 1,1 ': 2', 1 ''-bitriphenyl-4'-amine 5.0g Iodobenzene 9.2g Sodium tert-butoxide 5.9g Xylene 25ml Secondly add copper (I) iodide 0.4g, N, N 0.4 g of '-dimethylethylenediamine was heated, and it stirred at 125 degreeC for 8 hours. After cooling to room temperature, 100 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (toluene / n-hexane = 1/10) to obtain 6.6 g (yield 81%) of a pale yellow powder of Intermediate 1.

<Synthesis of Intermediate 2> [Chemical Formula 5] (Intermediate 2) Intermediate 2 is a polymer obtained by polymerizing Intermediate 1, which is a unit compound for introducing structural unit A, and is obtained by dibromizing Intermediate 1.

6.4 g of the previously synthesized intermediate 1 and 120 ml of tetrahydrofuran were added to a nitrogen-substituted reaction container, and 5.7 g of N-bromosuccinimide was added at room temperature, followed by stirring for 4 hours. Next, 180 ml of water was added, and the precipitated solid was collected by filtration. The obtained solid was washed with methanol to obtain 8.3 g of a white powder of Intermediate 2 (yield 93%).

<Synthesis of Intermediate 3> [Chemical Formula 6] (Intermediate 3) Intermediate 3 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

49.3 g of 3-aminobiphenyl and 300 ml of N, N-dimethylformamide were added to a reaction vessel substituted with nitrogen, and 54.4 g of N-bromosuccinimide was added at room temperature, followed by stirring for 5.5 hours. Next, water and toluene were added, and a liquid separation operation was performed to collect an organic layer. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (toluene / n-hexane = 1/1) to obtain 69.6 g (yield 96%) of an orange oil as intermediate 3.

<Synthesis of Intermediate 4> [Chemical Formula 7] (Intermediate 4) Intermediate 4 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. Intermediate 3 3.6g 4-biphenylborate 3.2g toluene 36ml ethanol 9ml 2M-potassium carbonate aqueous solution 11ml Next, 0.50g of triphenylphosphine palladium (0) was added and heated, and stirred at 75 ° C for 4 hours. After cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. This organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by crystallization using chloroform / methanol to obtain 2.6 g (yield 55%) of white powder such as intermediate 4.

<Synthesis of Intermediate 5> [Chemical Formula 8] (Intermediate 5) Intermediate 5 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. Intermediate 4 2.5g Iodobenzene 3.5g Sodium butanolate 2.2g 15 xylene 15ml Secondly add copper (I) iodide 0.2g, N, N'-dimethylethylenediamine 0.1g and heat, stir at 125 ° C 12 hours. After cooling to room temperature, 150 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (toluene / n-hexane = 1/10) to obtain 2.4 g (yield 65%) of white powder of Intermediate 5.

<Synthesis of Intermediate 6> [Chemical Formula 9] (Intermediate 6) Intermediate 6 is a polymer obtained by polymerizing Intermediate 5 which is a unit compound for introducing structural unit A, and is obtained by dibrominating the Intermediate 5.

2.4 g of the previously synthesized intermediate 5 and 50 ml of tetrahydrofuran were added to a reaction vessel substituted with nitrogen, and 1.8 g of N-bromosuccinimide was added at room temperature, followed by stirring for 4 hours. Next, 100 ml of water was added, and the precipitated solid was collected by filtration. The obtained solid was washed with methanol to obtain 3.1 g of a white powder of Intermediate 6 (yield 97%).

<Synthesis of Intermediate 7> [Chemical Formula 10] (Intermediate 7) Intermediate 7 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. 1-bromo-4- (naphthyl-2-yl) -benzene 10 g bis (pinacol) diboron 9.9 g potassium acetate 5.2 g 1,4-di 100 ml of alkane was followed by the addition of 0.87 g of methylene chloride adduct of 1,1'-bis (diphenylphosphino) ferrocene, palladium (II) dichloride, heating, and stirring at 90 ° C for 11.5 hours. After cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. This organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized using n-hexane to obtain 7.6 g (yield 66%) of an off-white powder of Intermediate 7.

<Synthesis of Intermediate 8> [Chemical Formula 11] (Intermediate 8) Intermediate 8 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. Intermediate 7 7.3g Intermediate 3 5.0g Toluene 48ml Ethanol 12ml 2M-potassium carbonate aqueous solution 16ml Next, 0.70g of triphenylphosphine palladium (0) was added and heated, and stirred at 75 ° C for 8 hours. After cooling to room temperature, water and toluene were added, and the organic layer was collected by a liquid separation operation. This organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized with methanol to obtain 4.1 g (yield 55%) of an off-white powder of Intermediate 8.

<Synthesis of Intermediate 9> [Chemical Formula 12] (Intermediate 9) Intermediate 9 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. Intermediate 8 g 4.0 g iodobenzene 5.3 g sodium tert-butoxide 3.1 g xylene 20 ml Next, 0.2 g of copper (I) iodide and 0.2 g of N, N'-dimethylethylenediamine were added and heated at 125 ° C. Stir for 10.5 hours. After cooling to room temperature, 150 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (toluene / n-hexane = 1/9) to obtain 4.5 g (yield 79%) of white powder of Intermediate 9.

<Synthesis of Intermediate 10> [Chemical Formula 13] (Intermediate 10) Intermediate 10 is a polymer obtained by polymerizing intermediate 9 which is a unit compound for introducing structural unit A, and is obtained by dibrominating the intermediate 9.

4.4 g of the previously synthesized intermediate 9 and 60 ml of tetrahydrofuran were added to a reaction vessel substituted with nitrogen, 3.0 g of N-bromosuccinimide was added at room temperature, and stirred for 6.5 hours. Next, 120 ml of water was added, and the precipitated solid was collected by filtration. The obtained solid was washed with methanol to obtain 5.7 g of a white powder of Intermediate 10 (yield: 99%).

<Synthesis of Intermediate 11> [Chemical Formula 14] (Intermediate 11) Intermediate 11 is an intermediate compound used for introduction of structural unit B owned by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. 2-Amino-9,9-n-dioctylfluorene 12.9g Iodobenzene 14.3g Sodium tert-butoxide 9.2g Xylene 20ml Next, 0.61g of copper (I) iodide, N, N'-dimethylethyl 0.57 g of diamine was heated and stirred at 125 ° C for 18 hours. After cooling to room temperature, 150 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (n-hexane) to obtain 14.5 g (yield 82%) of a yellow oil as intermediate 11.

<Synthesis of Intermediate 12> [Chemical Formula 15] (Intermediate 12) Intermediate 12 is an intermediate compound used for introduction of structural unit B owned by the high molecular weight compound of the present invention.

13.2 g of the previously synthesized intermediate 11 and 250 ml of tetrahydrofuran were added to a nitrogen-substituted reaction container, and 8.2 g of N-bromosuccinimide was added at room temperature, followed by stirring for 3 hours. 500 ml of water and 500 ml of toluene were added, and the organic layer was collected by a liquid separation operation. This organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (n-hexane) to obtain 17.0 g of a yellow oil of Intermediate 12 (yield 94%).

<Synthesis of Intermediate 13> [Chemical Formula 16] (Intermediate 13) Intermediate 13 is a polymer obtained by polymerizing Intermediate 11 which is a unit compound for introducing structural unit B, and is formed by diborating an intermediate 12.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. Intermediate 12 16.7 g bis (pinacol) diboron 11.9 g potassium acetate 5.7 g 1,4-di 170 ml of alkane was then added with 0.19 g of methylene chloride adduct of 1,1'-bis (diphenylphosphino) ferrocene, palladium (II) dichloride, heated, and stirred at 100 ° C for 7 hours. After cooling to room temperature, water and toluene were added, and the organic layer was collected by a liquid separation operation. This organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (ethyl acetate / n-hexane = 1/20) to obtain 7.6 g of a white powder of Intermediate 13 (yield 40%).

<Synthesis of Intermediate 14> [Chemical Formula 17] (Intermediate 14) Intermediate 14 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. 4- (naphthyl-1-yl) -phenylboronic acid 3.2g Intermediate 3 2.9g toluene 28ml ethanol 7ml 2M-potassium carbonate aqueous solution 9ml Next, 0.41g of triphenylphosphine palladium (0) was added and heated at 75 ° C Stir for 6 hours. After cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. This organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (chloroform / n-hexane = 1/1) to obtain 3.3 g (yield 76%) of a colorless transparent oil of Intermediate 14.

<Synthesis of Intermediate 15> [Chemical Formula 18] (Intermediate 15) Intermediate 15 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. Intermediate 14 3.1g Iodobenzene 3.7g Sodium tert-butoxide 2.4g Xylene 15ml Secondly add 0.16g of copper (I) iodide, 0.15g of N, N'-dimethylethylenediamine, heat and stir at 125 ° C 14.5 hours. After cooling to room temperature, 150 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (toluene / n-hexane = 1/9) to obtain 3.3 g of a white powder of Intermediate 15 (yield 76%).

<Synthesis of Intermediate 16> [Chem. 19] (Intermediate 16) Intermediate 16 is obtained by polymerizing intermediate unit 15 which is a unit compound for introducing structural unit A, and is obtained by dibrominating intermediate 15.

3.2 g of the previously synthesized intermediate 15 and 50 ml of tetrahydrofuran were added to a reaction vessel substituted with nitrogen, and 2.2 g of N-bromosuccinimide was added at room temperature, followed by stirring for 6 hours. Next, 100 ml of water and 300 ml of toluene were added, and the organic layer was collected by a liquid separation operation. This organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized with ethyl acetate / n-hexane = 1/10 to obtain 3.6 g of a white powder of Intermediate 16 (yield 87%).

<Synthesis of Intermediate 17> [Chemical Formula 20] (Intermediate 17) Intermediate 17 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. 2- (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-dimethylfluorene 5.7g intermediate 3 4.0g toluene 40 ml of ethanol, 10 ml of 2M-potassium carbonate aqueous solution, 12 ml, 0.56 g of triphenylphosphine palladium (0) was added, and the mixture was heated at 75 ° C. for 11 hours. After cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. This organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (chloroform / n-hexane = 1/1) to obtain 4.0 g (yield 69%) of a pale yellow powder of Intermediate 17.

<Synthesis of Intermediate 18> [Chemical Formula 21] (Intermediate 18) Intermediate 18 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. Intermediate 17 3.9g Iodobenzene 4.8g Sodium tert-butoxide 3.1g Xylene 20ml Secondly add 0.21g of copper (I) iodide, 0.19g of N, N'-dimethylethylenediamine, heat, and stir at 125 ° C 16 hours. After cooling to room temperature, 120 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (toluene / n-hexane = 1/9) to obtain 4.5 g of a white powder of Intermediate 18 (yield 81%).

<Synthesis of Intermediate 19> [Chemical Formula 22] (Intermediate 19) Intermediate 19 is used to polymerize Intermediate 18, which is a unit compound for introducing structural unit A, and is obtained by dibromizing Intermediate 18.

4.4 g of the previously synthesized intermediate 18 and 60 ml of tetrahydrofuran were added to a nitrogen-substituted reaction container, and 3.1 g of N-bromosuccinimide was added at room temperature, followed by stirring for 5 hours. Next, 120 ml of water was added, and the precipitated solid was collected by filtration. The obtained solid was washed with methanol to obtain 5.6 g of a white powder of Intermediate 19 (yield 97%).

<Synthesis of Intermediate 20> [Chemical Formula 23] (Intermediate 20) Intermediate 20 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. 6.2 g of 3-biphenylboronic acid, 6.2 g of intermediate, 3 g of 7.0 g, toluene, 72 ml of ethanol, 18 ml of 2M-potassium carbonate aqueous solution, and 22 ml of water. Next, 1.0 g of triphenylphosphine palladium (0) was added, and the mixture was stirred at 75 ° C for 5 hours. After allowing to cool to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was washed with methanol to obtain 6.5 g of an intermediate 20 as a white solid (yield 72%).

<Synthesis of Intermediate 21> [Chemical Formula 24] (Intermediate 21) Intermediate 21 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. Intermediate 20 6.4g Iodobenzene 9.0g Sodium tert-butoxide 5.7g Xylene 33ml Secondly add 0.4g of copper (I) iodide and 0.4g of N, N'-dimethylethylenediamine, and heat at 125 ° C Stir for 15 hours. After allowing to cool to room temperature, 240 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (toluene / n-hexane = 1/9) to obtain 8.3 g (yield 88%) of an off-white solid of Intermediate 21.

<Synthesis of Intermediate 22> [Chemical Formula 25] (Intermediate 22) Intermediate 22 is a polymer obtained by polymerizing intermediate 21 which is a unit compound for introducing structural unit A, and is obtained by dibromizing intermediate 21.

8.2 g of the previously synthesized intermediate 21 and 125 ml of tetrahydrofuran were added to a reaction vessel substituted with nitrogen, and 6.2 g of N-bromosuccinimide was added at room temperature, followed by stirring for 4 hours. 250 ml of water was added, and the precipitated solid was collected by filtration. The obtained solid was washed with methanol to obtain 10.6 g (yield 97%) of a white solid of Intermediate 22.

<Synthesis of Intermediate 23> [Chem. 26] (Intermediate 23) Intermediate 23 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. 19.0 g of 4-biphenylborate, 15.0 g of 3-bromoaniline, 15.0 g of toluene, 144 ml of ethanol, 36 ml of 2M-potassium carbonate aqueous solution, and 67 ml. Next, 3.0 g of triphenylphosphine palladium (0) was added, and the mixture was heated at 75 ° C. for 5 hours. After cooling to room temperature, the precipitated solid was collected by filtration, and washed with methanol. The obtained crude product was purified by column chromatography (toluene) to obtain 13.1 g of an off-white solid of Intermediate 23 (yield 61%).

<Synthesis of Intermediate 24> [Chemical Compound 27] (Intermediate 24) Intermediate 24 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

11.0 g of intermediate 23 and 170 ml of N, N-dimethylformamide were added to a reaction vessel substituted with nitrogen, and 8.0 g of N-bromosuccinimide was added at room temperature, followed by stirring for 2 hours. Water and toluene were added and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (chloroform / n-hexane = 1/1) to obtain 8.1 g (yield 59%) of the off-white solid of Intermediate 24.

<Synthesis of Intermediate 25> [Chemical Formula 28] (Intermediate 25) Intermediate 25 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. 2.2 g of 3-biphenylborate, 24 g of 3.3 g of toluene, 34 g of toluene, 34 ml of ethanol, 9 ml of 2M-potassium carbonate aqueous solution, and 8 ml. Next, 0.4 g of triphenylphosphine palladium (0) was added, and the mixture was stirred at 71 ° C. for 10 hours. After allowing to cool to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (toluene) to obtain 2.9 g of a pale yellow amorphous solid of Intermediate 12 (yield 71%).

<Synthesis of Intermediate 26> [Chemical Compound 29] (Intermediate 26) Intermediate 26 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. Intermediate 25 2.8g Iodobenzene 3.2g Sodium tert-butoxide 2.0g Xylene 14ml Secondly add 0.1g of copper (I) iodide, 0.1g of N, N'-dimethylethylenediamine, heat, and stir at 125 ° C 14 hours. After cooling to room temperature, 100 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (toluene / n-hexane = 1/9) to obtain 3.1 g (yield 80%) of an off-white solid of Intermediate 26.

<Synthesis of Intermediate 27> [Chemical Formula 30] (Intermediate 27) Intermediate 27 is obtained by polymerizing intermediate unit 26, which is a unit compound for introducing structural unit A, and is obtained by dibromizing intermediate 26.

3.0 g of the previously synthesized intermediate 26 and 45 ml of tetrahydrofuran were added to a reaction vessel substituted with nitrogen, and 2.0 g of N-bromosuccinimide was added at room temperature, followed by stirring for 4 hours. 90 ml of water was added, and the precipitated solid was collected by filtration. The obtained solid was washed with methanol to obtain 3.6 g of a white solid of Intermediate 27 (yield 92%).

<Synthesis of Intermediate 28> [Chem. 31] (Intermediate 28) Intermediate 28 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. 9,9-Dimethylphosphonium-2-boronic acid 38.1g 3-bromoaniline 25.0g toluene 240ml ethanol 60ml 2M-potassium carbonate aqueous solution 111ml Next, 5.0g triphenylphosphine palladium (0) was added and heated at 75 ° C Stir for 7 hours. After allowing to cool to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was washed with methanol to obtain 22.4 g of an intermediate 28 as a white solid (yield 54%).

<Synthesis of Intermediate 29> [Chemical Formula 32] (Intermediate 29) Intermediate 29 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

22.3 g of intermediate 28 and 340 ml of N, N-dimethylformamide were added to a reaction vessel substituted with nitrogen, and 13.9 g of N-bromosuccinimide was added at room temperature, followed by stirring for 3 hours. Water and chloroform were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (toluene) to obtain 24.6 g of an off-white solid of Intermediate 29 (yield 87%).

<Synthesis of Intermediate 30> [Chemical Formula 33] (Intermediate 30) Intermediate 30 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. 4-biphenylborate 4.8 g intermediate 29 8.0 g toluene toluene 84 ml ethanol 21 ml 2M-potassium carbonate aqueous solution 17 ml Next, 0.5 g of triphenylphosphine palladium (0) was added and heated, and stirred at 73 ° C. for 5 hours. After allowing to cool to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (chloroform / n-hexane = 1/4) to obtain 8.3 g of a brown amorphous solid of Intermediate 30 (yield 77%).

<Synthesis of Intermediate 31> [Chem. 34] (Intermediate 31) Intermediate 31 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. Intermediate 30 8.2g Iodobenzene 8.4g Sodium tert-butoxide 5.4g Xylene 40ml Secondly add 0.4g of copper (I) iodide, 0.3g of N, N'-dimethylethylenediamine, and heat at 125 ° C Stir for 18 hours. After cooling to room temperature, 250 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (toluene / n-hexane = 1/4) to obtain 4.6 g (yield 41%) of a white amorphous solid of Intermediate 31.

<Synthesis of Intermediate 32> [Chem. 35] (Intermediate 32) Intermediate 32 is obtained by polymerizing intermediate 31, which is a unit compound for introducing structural unit A, and is obtained by dibromizing intermediate 31.

4.4 g of the previously synthesized intermediate 31 and 65 ml of tetrahydrofuran were added to a nitrogen-substituted reaction container, and 2.7 g of N-bromosuccinimide was added at room temperature, followed by stirring for 5 hours. 130 ml of water was added, and the precipitated solid was collected by filtration. The obtained solid was washed with methanol to obtain 3.9 g of a white solid of Intermediate 32 (yield 70%).

<Synthesis of Intermediate 33> [Chemical Formula 36] (Intermediate 33) Intermediate 33 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. 4.9 g of 9,9-dimethylphosphonium-2-boronic acid, 29 g of 7.7 g of intermediate, 84 ml of toluene, 84 ml of ethanol, 21 ml of 2M-potassium carbonate aqueous solution, 16 ml, 0.5 g of triphenylphosphine palladium (0) was added, and the mixture was stirred at 73 ° C for 6 hours. hour. After allowing to cool to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (ethyl acetate / n-hexane = 1/4) to obtain 7.7 g (yield 70%) of a pale yellow solid of Intermediate 33.

<Synthesis of Intermediate 34> [Chem. 37] (Intermediate 34) Intermediate 34 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. Intermediate 33 7.6g Iodobenzene 7.1g Sodium tert-butoxide 4.6g Xylene 38ml Secondly add 0.3g of copper (I) iodide, 0.3g of N, N'-dimethylethylenediamine and heat, stir at 125 ° C 28 hours. After cooling to room temperature, 250 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (toluene / n-hexane = 1/9) to obtain 2.9 g (yield 29%) of an off-white solid of Intermediate 34.

<Synthesis of Intermediate 35> [Chemical Formula 38] (Intermediate 35) Intermediate 35 is a polymer obtained by polymerizing intermediate 34, which is a unit compound for introducing structural unit A, and is obtained by dibromizing intermediate 34.

2.7 g of the previously synthesized intermediate 34 and 60 ml of tetrahydrofuran were added to a reaction vessel substituted with nitrogen, and 1.6 g of N-bromosuccinimide was added at room temperature, and stirred for 5 hours. Water and toluene were added and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was dispersed and washed with methanol to obtain 3.1 g (yield 99%) of a white solid of Intermediate 35.

<Synthesis of Intermediate 36> [Chemical Formula 39] (Intermediate 36) Intermediate 36 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. Naphthalene-2-borate -2- 55.0 g 3-bromoaniline 50.0 g toluene 480 ml ethanol 120 ml 2M-potassium carbonate aqueous solution 223 ml Next, 1.7 g of triphenylphosphine palladium (0) was added and heated, and stirred at 75 ° C. for 7 hours. After allowing to cool to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was washed with hexane to obtain 55.5 g of an off-white solid of Intermediate 36 (yield 87%).

<Synthesis of Intermediate 37> [Chemical Formula 40] (Intermediate 37) Intermediate 37 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

55.4 g of intermediate 36 and 554 ml of N, N-dimethylformamide were added to a reaction vessel substituted with nitrogen, 45.0 g of N-bromosuccinimide was added at room temperature, and stirred for 4 hours. Water and toluene were added and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (toluene) to obtain 51.1 g of a reddish brown oil of Intermediate 37 (yield 66%).

<Synthesis of Intermediate 38> [Chem. 41] (Intermediate 38) Intermediate 38 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. Intermediate 37 6.4g Intermediate 7 7.6g Toluene 55ml Ethanol 14ml 2M-potassium carbonate aqueous solution 16ml Next, 0.2g of triphenylphosphine palladium (0) was added and heated, followed by stirring at 73 ° C for 10 hours. After allowing to cool to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 6.0 g (yield 69%) of an orange solid of Intermediate 38.

<Synthesis of Intermediate 39> [Chem. 42] (Intermediate 39) Intermediate 39 is an intermediate compound used for introduction of structural unit A possessed by the high molecular weight compound of the present invention.

The following components were added to a reaction vessel substituted with nitrogen. Intermediate 38 6.0g Iodobenzene 6.3g Sodium tert-butoxide 4.1g Xylene 30ml Secondly add 0.3g of copper (I) iodide, 0.3g of N, N'-dimethylethylenediamine and heat, stir at 125 ° C 17 hours. After allowing to cool to room temperature, 190 ml of toluene was added, stirred for 1 hour, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography (toluene / n-hexane = 1/9) to obtain 4.4 g (yield 54%) of a white solid of Intermediate 39.

<Synthesis of Intermediate 40> [Chemical Formula 43] (Intermediate 40) The intermediate 40 is a polymer obtained by polymerizing the intermediate 39, which is a unit compound for introducing the structural unit A, and is obtained by dibromizing the intermediate 39.

4.3 g of the previously synthesized intermediate 39 and 100 ml of tetrahydrofuran were added to a reaction vessel substituted with nitrogen, and 2.6 g of N-bromosuccinimide was added at room temperature, followed by stirring for 8 hours. Water and toluene were added and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was washed with methanol to obtain 4.8 g of a white solid of Intermediate 40 (yield 89%).

<Synthesis of Intermediate 41> [Chemical Formula 44] (Intermediate 41) The intermediate 41 is an intermediate compound for introducing the structural unit B.

The following components were added to a nitrogen-substituted reaction container, and nitrogen was bubbled in for 30 minutes. 1,4-dibromo-2,5-bis (n-hexyl) benzene 10.0 g bis (pinacol) diboron 13.8 g potassium acetate 7.3 g 1,4-di Next, 100 ml of alkane was added with 0.4 g of methylene chloride adduct of 1,1'-bis (diphenylphosphino) ferrocene, palladium (II) dichloride, and the mixture was heated at 90 ° C for 10 hours. After cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. This organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product. The obtained crude product was washed with methanol to obtain 10.7 g (yield 99%) of an off-white solid of Intermediate 41.

<Example 1> Synthesis of high molecular weight compound A; The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 2.9g middle Body 2 2.0g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.4g Tripotassium phosphate 4.0g Toluene 9ml Water 5ml 1,4-Di To 27 ml of alkane, 3.3 mg of palladium (II) acetate and 26.7 mg of tri-o-tolylphosphine were added, followed by heating and stirring at 86 ° C for 6.5 hours. 52 mg of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octyl Rinse, stir for 0.5 hour, then add 140 mg of bromobenzene, and stir for 0.5 hour. 80 ml of toluene and 80 ml of a 5 wt% aqueous solution of sodium N, N-diethyldithiosulfate were added and heated, followed by stirring under reflux for 2 hours. After cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, and the silica gel was filtered and removed. The obtained filtrate was concentrated under reduced pressure, 50 ml of tetrahydrofuran was added to the dried solid to dissolve it, and it was added dropwise to 400 ml of methanol, and the obtained precipitate was collected by filtration. This operation was repeated twice and dried to obtain 2.9 g of a high molecular weight compound A (yield 84%).

The obtained high molecular weight compound A was subjected to NMR measurement. ^The results of ¹ H-NMR measurement are shown in FIG. 58. The average molecular weight, dispersion, and chemical composition of high molecular weight compounds measured by GPC are as follows. Number average molecular weight Mn (polystyrene equivalent): 42,000 Weight average molecular weight Mw (polystyrene equivalent): 116,000 Dispersion (Mw / Mn): 2.8 Chemical composition: [Chemical 45] (High molecular weight compound A)

It can be understood from the above chemical composition that this high molecular weight compound A contains 43 mol% of the structural unit A represented by the general formula (1), 47 mol% of the structural unit B which improves the solubility to organic solvents, and contains 10 Molar% is used for the structural unit C which improves thermal crosslinkability.

<Example 2> Synthesis of high molecular weight compound B; The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 3.6g middle Body 6 2.8g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.5g Tripotassium phosphate 5.0g Toluene 13ml Water 7ml 1,4-Di 39 ml of alkane was followed by the addition of 2.0 mg of palladium (II) acetate and 16.7 mg of tri-o-tolylphosphine, followed by heating and stirring at 85 ° C for 6 hours. Then 65 mg of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octyl Rinse, stir for 1 hour, then add 180 mg of bromobenzene, and stir for 1 hour. 100 ml of toluene and 100 ml of a 5 wt% aqueous solution of sodium N, N-diethyldithiocarbamate were added and heated, followed by stirring under reflux for 2 hours. After cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, filtration, and removal of the silica gel. The obtained filtrate was concentrated under reduced pressure, 150 ml of tetrahydrofuran was added to the dried solid and dissolved, and the solution was added dropwise to 300 ml of methanol, and the obtained precipitate was filtered. This operation was repeated twice and dried to obtain 4.5 g of a high molecular weight compound B (yield 96%).

NMR measurement was performed on the obtained high molecular weight compound B. ^The results of ¹ H-NMR measurement are shown in FIG. 59. The average molecular weight, dispersion, and chemical composition of high molecular weight compounds measured by GPC are as follows. Number average molecular weight Mn (polystyrene equivalent): 70,000 Weight average molecular weight Mw (polystyrene equivalent): 427,000 Dispersion (Mw / Mn): 6.1 Chemical composition: [Chem. 46] (High molecular weight compound B)

It can be understood from the above chemical composition that this high molecular weight compound A contains 42 mol% of the structural unit A represented by the general formula (1), and 48 mol% of the structural unit B which improves the solubility in organic solvents. In addition, the amount of 10 mol% contains the structural unit C that improves thermal crosslinkability.

<Example 3> Synthesis of high molecular weight compound C; The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 6.5g middle Volume 10 5.5g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.87g Tripotassium phosphate 9.0g toluene 16ml water 9ml 1,4-dioxane 48 ml of alkane was added with 1.9 mg of palladium (II) acetate and 15.0 mg of tri-o-tolylphosphine, heated, and stirred at 88 ° C for 10 hours. Thereafter, 22 mg of phenylboronic acid was added and stirred for 1 hour, followed by 0.32 g of bromobenzene and stirred for 1 hour. 100 ml of toluene and 100 ml of a 5 wt% aqueous solution of sodium N, N-diethyldithiocarbamate were added and heated, followed by stirring under reflux for 2 hours. After cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, and the silica gel was filtered and removed. The obtained filtrate was concentrated under reduced pressure, 300 ml of toluene was added to the dried solid to dissolve it, and 600 ml of n-hexane was added dropwise, and the obtained precipitate was collected by filtration. This operation was repeated 3 times and allowed to dry to obtain 8.0 g of a high molecular weight compound C (yield 92%).

The obtained high molecular weight compound C was subjected to NMR measurement. ^The results of ¹ H-NMR measurement are shown in FIG. 60. The average molecular weight, dispersion, and chemical composition of high molecular weight compounds measured by GPC are as follows. Number average molecular weight Mn (polystyrene equivalent): 45,000 Weight average molecular weight Mw (polystyrene equivalent): 97,000 Dispersion (Mw / Mn): 2.1 Chemical composition: [Chem. 47] (High molecular weight compound C)

It can be understood from the above chemical composition that this high molecular weight compound A contains 41 mol% of the structural unit A represented by the general formula (1) and 49 mol% of the structural unit B which improves the solubility to organic solvents, and The content of 10 mol% contains the structural unit C which improves thermal crosslinkability.

<Example 4> Synthesis of high molecular weight compound D; The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. Intermediate 13 3.7g Intermediate 10 2.5g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.4g Tripotassium phosphate 4.1g Toluene 9ml Water 5ml 1 , 4-two To 27 ml of alkane, 1.7 mg of palladium (II) acetate and 13.6 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 88 ° C for 10 hours. Then 67 mg of Intermediate 13 was added and stirred for 1 hour, followed by 0.14 g of bromobenzene and stirred for 1 hour. 50 ml of toluene and 50 ml of a 5 wt% N, N-diethyldithiosulfate aqueous solution were added and heated, followed by stirring under reflux for 2 hours. After cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, filtration, and removal of the silica gel. The obtained filtrate was concentrated under reduced pressure, 150 ml of toluene was added to the dried solid to dissolve it, and 150 ml of n-hexane was added dropwise, and the obtained precipitate was collected by filtration. This operation was repeated 3 times and dried to obtain 3.9 g of a high molecular weight compound D (yield 87%).

The obtained high molecular weight compound D was subjected to NMR measurement. ^The results of ¹ H-NMR measurement are shown in FIG. 61. The average molecular weight, dispersion, and chemical composition of high molecular weight compounds measured by GPC are as follows. Number average molecular weight Mn (polystyrene equivalent): 51,000 Weight average molecular weight Mw (polystyrene equivalent): 127,000 Dispersion (Mw / Mn): 2.5 Chemical composition: [Chem. 48] (High molecular weight compound D)

It can be understood from the above chemical composition that this high molecular weight compound D contains 43 mol% of the structural unit A represented by the general formula (1), and 49 mol% of the structural unit B which improves the solubility to organic solvents, and It contains the structural unit C which improves thermal crosslinkability in an amount of 8 mol%.

<Example 5> Synthesis of high molecular weight compound E; The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 4.1g middle Volume 16 3.5g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.55g Tripotassium phosphate 5.7g Toluene 16ml Water: 9ml 1,4-Di Alkane: 48 ml Next, 2.3 mg of palladium (II) acetate and 19.0 mg of tri-o-tolylphosphine were added and heated, followed by stirring at 86 ° C for 8 hours. 74 mg of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octyl Rinse, stir for 1 hour, then add 0.2 g of bromobenzene and stir for 1 hour. 100 ml of toluene and 100 ml of a 5 wt% aqueous solution of sodium N, N-diethyldithiocarbamate were added and heated, followed by stirring under reflux for 2 hours. After cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, filtration, and removal of the silica gel. The obtained filtrate was concentrated under reduced pressure, 150 ml of tetrahydrofuran was added to the dried solid to dissolve it, and 300 ml of methanol was added dropwise, and the obtained precipitate was collected by filtration. This operation was repeated twice and dried to obtain 5.2 g of a high molecular weight compound E (yield 94%).

The obtained high molecular weight compound E was subjected to NMR measurement. ^The results of ¹ H-NMR measurement are shown in FIG. 62. The average molecular weight, dispersion, and chemical composition of high molecular weight compounds measured by GPC are as follows. Number average molecular weight Mn (polystyrene equivalent): 45,000 Weight average molecular weight Mw (polystyrene equivalent): 115,000 Dispersion (Mw / Mn): 2.6 Chemical composition: [Chemical 49] (High molecular weight compound E)

It can be understood from the above chemical composition that this high molecular weight compound E contains 41 mol% of the structural unit A represented by the general formula (1), and 49 mol% of the structural unit B which improves the solubility in organic solvents, and The content of 10 mol% contains the structural unit C which improves thermal crosslinkability.

<Example 6> Synthesis of high molecular weight compound F; The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 6.5g middle Volume 19 5.4g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.87g Tripotassium phosphate 9.0g Toluene 16ml Water 9ml 1,4-Di 48 ml of alkane was added with 1.9 mg of palladium (II) acetate and 115.0 mg of tri-o-tolylphosphine, heated, and stirred at 86 ° C for 10 hours. Then add 0.12g of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octyl After stirring for 1 hour, 0.32 g of bromobenzene was added next, followed by stirring for 1 hour. 100 ml of toluene and 100 ml of a 5 wt% aqueous solution of sodium N, N-diethyldithiocarbamate were added and heated, followed by stirring under reflux for 2 hours. Next, after cooling to room temperature, saturated brine and toluene were added, and the organic layer was collected by a liquid separation operation. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, filtration, and removal of the silica gel. The obtained filtrate was concentrated under reduced pressure, 200 ml of tetrahydrofuran was added to the dried solid to dissolve it, and it was added dropwise to 400 ml of methanol, and the obtained precipitate was collected by filtration. This operation was repeated twice and dried to obtain 8.4 g of a high molecular weight compound F (yield 96%).

The obtained high molecular weight compound F was subjected to NMR measurement. ^The results of ¹ H-NMR measurement are shown in FIG. 63. The average molecular weight, dispersion, and chemical composition of high molecular weight compounds measured by GPC are as follows. Number average molecular weight Mn (polystyrene equivalent): 75,000 weight average molecular weight Mw (polystyrene equivalent): 382,000 Dispersion (Mw / Mn): 5.1 Chemical composition: [Chemical 50] (High molecular weight compound F)

It can be understood from the above chemical composition that this high molecular weight compound F contains 43 mol% of structural unit A represented by the general formula (1), 48 mol% of structural unit B which improves the solubility to organic solvents, and It contains the structural unit C which improves thermal crosslinkability in an amount of 9 mol%.

<Example 7> Synthesis of high molecular weight compound G: The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 6.5g middle Volume 22 5.1g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.9g Tripotassium phosphate 9.0g Toluene 16ml 1,4-Di 48 ml of alkane and 9 ml of water were added, followed by 2.0 mg of palladium (II) acetate and 16.7 mg of tri-o-tolylphosphine, followed by heating at 85 ° C for 7.5 hours. Further added 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 120mg Stir for 1 hour, add 320 mg of bromobenzene, and stir for 1 hour. 100 ml of toluene and 100 ml of a 5 wt% N, N-diethyldithiosulfate aqueous solution were added and heated, followed by stirring under reflux for 1 hour. After cooling to room temperature, a liquid separation operation was performed to collect an organic layer, and the organic layer was washed twice with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, filtration, and removal of the silica gel. The obtained filtrate was concentrated under reduced pressure, 200 ml of tetrahydrofuran was added to the dried solid to dissolve it, and it was added dropwise to 400 ml of methanol, and the obtained precipitate was collected by filtration. This operation was repeated twice and dried to obtain 8.0 g of a high molecular weight compound G (yield 94%).

The obtained high molecular weight compound G was subjected to NMR measurement. ^The results of ¹ H-NMR measurement are shown in FIG. 64. The average molecular weight, dispersion, and chemical composition of high molecular weight compounds measured by GPC are as follows. Average molecular weight Mn (polystyrene equivalent): 52,000 Weight average molecular weight Mw (polystyrene equivalent): 150,000 Dispersion (Mw / Mn): 2.9 Chemical composition: [Chem. 51] (High molecular weight compound G)

It can be understood from the above chemical composition that this high molecular weight compound G contains 47 mol% of structural unit A represented by the general formula (1), and 43 mol% of structural unit B which improves the solubility to organic solvents, and It contains the structural unit C which improves thermal crosslinkability in an amount of 9 mol%.

<Example 8> Synthesis of high molecular weight compound H: The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 3.8g middle 27 3.3g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.5g Tripotassium phosphate 5.3g Toluene 10ml 1,4-Di 30 ml of alkane and 5 ml of water were added, followed by 1.0 mg of palladium (II) acetate and 8.8 mg of tri-o-tolylphosphine, followed by heating and stirring at 85 ° C for 10 hours. Further, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 70 mg After stirring for 1 hour, 180 mg of bromobenzene was added and stirred for 1 hour. 100 ml of toluene and 100 ml of a 5 wt% N, N-diethyldithiosulfate aqueous solution were added and heated, followed by stirring under reflux for 1 hour. After cooling to room temperature, a liquid separation operation was performed to collect an organic layer, and the organic layer was washed twice with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, filtration, and removal of the silica gel. The obtained filtrate was concentrated under reduced pressure, 150 ml of tetrahydrofuran was added to the dried solid to dissolve it, and 300 ml of methanol was added dropwise, and the obtained precipitate was collected by filtration. This operation was repeated twice and dried to obtain 1.0 mg of a high molecular weight compound H (yield 94%).

The obtained high molecular weight compound H was subjected to NMR measurement. ^The results of ¹ H-NMR measurement are shown in FIG. 65. The average molecular weight, dispersion, and chemical composition measured by GPC of high molecular weight compounds are as follows: average molecular weight Mn (polystyrene equivalent): 39,000 weight average molecular weight Mw (polystyrene equivalent): 85,000 dispersion (Mw / Mn): 2.2 Chemical composition: [Chem. 52] (High molecular weight compound H)

It can be understood from the above chemical composition that this high molecular weight compound H contains 47 mol% of structural unit A represented by the general formula (1), 44 mol% of structural unit B which improves the solubility in organic solvents, and It contains the structural unit C which improves thermal crosslinkability in an amount of 9 mol%.

<Example 9> Synthesis of high molecular weight compound I: The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 3.5g middle 32 3.3 g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.5 g tripotassium phosphate 4.9 g toluene 14 ml 1,4-di 42 ml of alkane and 8 ml of water were added, followed by 4.0 mg of palladium (II) acetate and 32.3 mg of tri-o-tolylphosphine, followed by heating at 85 ° C for 6 hours. Furthermore, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 63 mg After stirring for 1 hour, 171 mg of bromobenzene was added and stirred for 1 hour. 100 ml of toluene and 100 ml of a 5 wt% N, N-diethyldithiosulfate aqueous solution were added and heated, followed by stirring under reflux for 1 hour. After cooling to room temperature, a liquid separation operation was performed to collect an organic layer, and the organic layer was washed twice with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, filtration, and removal of the silica gel. The obtained filtrate was concentrated under reduced pressure, 120 ml of toluene was added to the dried solid to dissolve it, and 240 ml of hexane was added dropwise, and the obtained precipitate was collected by filtration. This operation was repeated twice and dried to obtain 4.7 g of a high molecular weight compound I (yield 92%).

The obtained high molecular weight compound I was subjected to NMR measurement. ^The results of ¹ H-NMR measurement are shown in FIG. 66. The average molecular weight, dispersion, and chemical composition measured by GPC of the high molecular weight compound are as follows: average molecular weight Mn (polystyrene equivalent): 63,000 weight average molecular weight Mw (polystyrene equivalent): 479,000 dispersion (Mw / Mn): 7.7 Chemical composition: [Chem. 53] (High molecular weight compound I)

It can be understood from the above chemical composition that this high molecular weight compound I contains 46 mol% of structural unit A represented by the general formula (1), 46 mol% of structural unit B which improves the solubility to organic solvents, and It contains the structural unit C which improves thermal crosslinkability in an amount of 8 mol%.

<Example 10> Synthesis of high molecular weight compound J: The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 3.1g middle Body 35 3.0g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.4g Tripotassium phosphate 4.3g Toluene 16ml 1,4-Di 48 ml of alkane and 9 ml of water were added, followed by 3.5 mg of palladium (II) acetate and 28.6 mg of tri-o-tolylphosphine, followed by heating at 85 ° C for 5 hours. Further added 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 56mg After stirring for 1 hour, 150 mg of bromobenzene was added and stirred for 1 hour. 100 ml of toluene and 100 ml of a 5 wt% N, N-diethyldithiosulfate aqueous solution were added and heated, followed by stirring under reflux for 1 hour. After cooling to room temperature, a liquid separation operation was performed to collect an organic layer, and the organic layer was washed twice with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, filtration, and removal of the silica gel. The obtained filtrate was concentrated under reduced pressure, 120 ml of toluene was added to the dried solid to dissolve it, and 240 ml of hexane was added dropwise, and the obtained precipitate was collected by filtration. This operation was repeated twice and dried to obtain 4.2 g of a high molecular weight compound J (yield 90%).

The obtained high molecular weight compound J was subjected to NMR measurement. ^The results of ¹ H-NMR measurement are shown in FIG. 67. The average molecular weight, dispersion, and chemical composition measured by GPC of high molecular weight compounds are as follows: average molecular weight Mn (polystyrene equivalent): 61,000 weight average molecular weight Mw (polystyrene equivalent): 183,000 dispersion (Mw / Mn): 3.0 Chemical composition: [Chem. 54] (High molecular weight compound J)

It can be understood from the above chemical composition that this high molecular weight compound J contains 46 mol% of structural unit A represented by the general formula (1), 45 mol% of structural unit B which improves the solubility to organic solvents, and It contains the structural unit C which improves thermal crosslinkability in an amount of 9 mol%.

<Example 11> Synthesis of high molecular weight compound K: The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 4.5g middle Body 40 4.1g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.6g Tripotassium phosphate 6.2g Toluene 18ml 1,4-Di 54 ml of alkane and 10 ml of water were added, followed by 5.1 mg of palladium (II) acetate and 41.6 mg of tri-o-tolylphosphine, followed by heating at 85 ° C for 5 hours. Further, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxolane-2-yl) -9,9-di-n-octylfluorene 80 mg Stir for 1 hour, add 220 mg of bromobenzene, and stir for 1 hour. 100 ml of toluene and 100 ml of a 5 wt% N, N-diethyldithiosulfate aqueous solution were added and heated, followed by stirring under reflux for 1 hour. After cooling to room temperature, a liquid separation operation was performed to collect an organic layer, and the organic layer was washed twice with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, filtration, and removal of the silica gel. The obtained filtrate was concentrated under reduced pressure, 150 ml of toluene was added to the dried solid to dissolve it, and 300 ml of hexane was added dropwise, and the obtained precipitate was collected by filtration. This operation was repeated twice and dried to obtain 6.1 g of a high molecular weight compound K (yield 94%).

The obtained high molecular weight compound K was subjected to NMR measurement. ^{The 1} H-NMR measurement result is shown in FIG. 68. The average molecular weight, dispersion, and chemical composition measured by GPC of the high molecular weight compound are as follows: average molecular weight Mn (polystyrene equivalent): 66,000 weight average molecular weight Mw (polystyrene equivalent): 211,000 dispersion (Mw / Mn): 3.2 Chemical composition: [Chem 55] (High molecular weight compound K)

It can be understood from the above chemical composition that this high molecular weight compound K contains a structural unit A represented by the general formula (1) of 40 mol%, and a structural unit B of 50 mol% which improves the solubility in organic solvents, and It contains the structural unit C which improves thermal crosslinkability in an amount of 10 mol%.

<Example 12> Synthesis of high molecular weight compound L: The following components were added to a reaction vessel substituted with nitrogen, and nitrogen was bubbled in for 30 minutes. Intermediate 41 5.0g Intermediate 10 5.5g N, N-bis (4-bromophenyl) -N- (benzocyclobuten-4-yl) -amine 0.9g Tripotassium phosphate 8.9g Toluene 12ml 1,4 -two 36 ml of alkane, 7 ml of water, 1.8 mg of palladium (II) acetate and 14.9 mg of tri-o-tolylphosphine were added, heated, and stirred at 85 ° C for 9 hours. Furthermore, 90 mg of intermediate 41 was added and stirred for 1 hour, and 320 mg of bromobenzene was added and stirred for 1 hour. 100 ml of toluene and 100 ml of a 5 wt% N, N-diethyldithiosulfate aqueous solution were added and heated, followed by stirring under reflux for 1 hour. After cooling to room temperature, a liquid separation operation was performed to collect an organic layer, and the organic layer was washed twice with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added, followed by adsorption purification, filtration, and removal of the silica gel. The obtained filtrate was concentrated under reduced pressure, 130 ml of toluene was added to the dried solid to dissolve it, and the solution was added dropwise to 260 ml of hexane, and the obtained precipitate was collected by filtration. This operation was repeated twice and dried to obtain 6.6 g of a high molecular weight compound L (yield 90%).

The obtained high molecular weight compound L was subjected to NMR measurement. ^The results of ¹ H-NMR measurement are shown in FIG. 69. The average molecular weight, dispersion, and chemical composition measured by GPC of high molecular weight compounds are as follows: average molecular weight Mn (polystyrene equivalent): 38,000 weight average molecular weight Mw (polystyrene equivalent): 78,000 dispersion (Mw / Mn): 2.0 Chemical composition: [Chem. 56] (High molecular weight compound L)

It can be understood from the above chemical composition that the high molecular weight compound L contains a structural unit A represented by the general formula (1) of 40 mol%, and a structural unit B of 50 mol% which improves the solubility to an organic solvent, and It contains the structural unit C which improves thermal crosslinkability in an amount of 10 mol%.

<Example 13> A high-molecular-weight compound A to L synthesized in Examples 1 to 12 was used to produce a 100-nm-thick vapor-deposited film on an ITO substrate, and a free potential measuring device (manufactured by Sumitomo Heavy Industries, Ltd., PYS) -202 type) measure work function. The results are as follows. Work function High molecular weight compound A (polymer) 5.65eV High molecular weight compound B (polymer) 5.59eV High molecular weight compound C (polymer) 5.59eV High molecular weight compound D (polymer) 5.40eV High molecular weight compound E (polymer) 5.59eV high molecular weight compound F (polymer) 5.57eV high molecular weight compound G (polymer) 5.59eV high molecular weight compound H (polymer) 5.59eV high molecular weight compound I (polymer) 5.58eV high molecular weight compound J (polymer) 5.55eV high molecular weight compound K (polymer) 聚合物 5.58eV high molecular weight compound L (polymer) 5.73eV

The high-molecular-weight compounds A to L of the present invention have a better energy level than a work function of 5.4 eV carried by general hole transport materials such as NPD and TPD, and it is known that the hole transport ability is good.

<Example 14> Production and evaluation of organic EL device; An organic EL device having a layer structure as shown in FIG. 57 was produced by the following method.

Specifically, the ITO glass substrate 1 having a film thickness of 50 nm was washed with an organic solvent, and then the surface of the ITO was washed with UV / ozone treatment. The compound of the following structural formula (Solvay, AQ-1200) was formed to a thickness of 55 nm by a spin coating method so as to cover the transparent anode 2 (ITO) provided on the glass substrate 1, and was heated at 170 ° C on a hot plate. It dried for 10 minutes, and the hole injection layer 3 was formed. [Chemical] 57 (AQ1200)

The high molecular weight compound A obtained in Example 1 was dissolved in toluene to 0.6% by weight to prepare a coating solution. Move the substrate on which the hole injection layer 3 has been formed as described above, into a glove box replaced with dry nitrogen, and on the hole injection layer 3, use the coating solution to form a 20 nm thick coating layer by spin coating. Then, it was dried on a hot plate at 200 ° C. for 10 minutes to form a hole transporting layer 4.

The substrate on which the hole transport layer 4 has been formed as described above is installed in a vacuum evaporation machine, and the pressure is reduced to 0.001 Pa or less. A light-emitting layer 5 having a thickness of 40 nm was formed on the hole transporting layer 4 by binary evaporation of SBD2460 (EMD-1) manufactured by SFC Corporation and ABH401 (EMH-1) manufactured by SFC Corporation. In the binary vapor deposition, the vapor deposition rate ratio was set to EMD-1: EMH-1 = 7: 93.

Compounds (ETM-1) and (ETM-2) of the following structural formulas were prepared as electron transport materials. [Chemical] 58 (ETM-1) (ETM-2)

On the light-emitting layer 5 formed as described above, an electron transport material 6 having a film thickness of 20 nm was formed by binary evaporation using the above-mentioned electron transport materials (ETM-1) and (ETM-2). In the binary vapor deposition, the vapor deposition rate ratio was set to ETM-1: ETM-2 = 50: 50.

Finally, aluminum was vapor-deposited to a thickness of 100 nm to form a cathode 7. In this way, the glass substrate on which the transparent anode 2, the hole injection layer 3, the hole transport layer 4, the light emitting layer 5, the electron transport material 6, and the cathode 7 have been formed is moved to a glove box replaced with dry nitrogen, and UV is used. The hardening resin is bonded to other glass substrates for sealing, and an organic EL element is produced. For the produced organic EL element, characteristics were measured at normal temperature in the atmosphere. In addition, the light emission characteristics when a DC voltage was applied to the produced organic EL element were measured. The measurement results are shown in Table 1.

<Example 15> The hole transporting layer 4 was formed by using a coating solution prepared by replacing the high molecular weight compound A with the compound of high molecular weight B (high molecular weight compound B) in 0.6% by weight in toluene. It carried out exactly like Example 14 and produced the organic EL element. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Example 16> The hole transporting layer 4 was formed by using a coating solution prepared by replacing the high molecular weight compound A with the compound of Example 3 (high molecular weight compound C) and dissolving it in toluene to 0.6% by weight. An organic EL device was produced in the same manner as in Example 14. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Example 17> The hole transporting layer 4 was formed by using a coating solution prepared by replacing the high molecular weight compound A with the compound of Example 4 (high molecular weight compound D) and dissolving it in toluene to 0.6% by weight. It carried out exactly like Example 14 and produced the organic EL element. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Example 18> The hole transporting layer 4 was formed using a coating solution prepared by replacing the high molecular weight compound A with the compound of Example 5 (high molecular weight compound E) and dissolving it in toluene to 0.6% by weight. An organic EL device was produced in the same manner as in Example 14. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Example 19> The hole transporting layer 4 was formed by using a coating solution prepared by replacing the high molecular weight compound A with the compound of Example 6 (high molecular weight compound F) and dissolving it in toluene to 0.6% by weight. It carried out exactly like Example 14 and produced the organic EL element. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Example 20> The hole transporting layer 4 was formed by using a coating liquid prepared by replacing the high molecular weight compound A with the compound of Example 7 (high molecular weight compound G) and dissolving it in toluene to 0.6% by weight. It carried out exactly like Example 14 and produced the organic EL element. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Example 21> The hole transporting layer 4 was formed by using a coating liquid prepared by replacing the high molecular weight compound A with the compound of Example 8 (high molecular weight compound H) and dissolving it in toluene to 0.6% by weight. It carried out exactly like Example 14 and produced the organic EL element. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Example 22> The hole transporting layer 4 was formed by using a coating liquid prepared by replacing the high molecular weight compound A with the compound of high molecular weight compound (high molecular weight compound I) in Example 9 and dissolving it in toluene to 0.6% by weight. It carried out exactly like Example 14 and produced the organic EL element. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Example 23> The hole transporting layer 4 was formed by using a coating solution prepared by replacing the high molecular weight compound A with the compound of Example 10 (high molecular weight compound J) and dissolving it in toluene to 0.6% by weight. It carried out exactly like Example 14 and produced the organic EL element. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Example 24> The hole transporting layer 4 was formed by using a coating solution prepared by replacing the high molecular weight compound A with the compound of Example 11 (high molecular weight compound K) and dissolving it in toluene to 0.6% by weight. It carried out exactly like Example 14 and produced the organic EL element. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Example 25> The hole transporting layer 4 was formed by using a coating liquid prepared by replacing the high molecular weight compound A with the compound of high molecular weight L in Example 12 (high molecular weight compound L) and dissolving it in toluene to 0.6% by weight. It carried out exactly like Example 14 and produced the organic EL element. For the produced organic EL device, characteristics were measured at normal temperature in the atmosphere. Table 1 shows the measurement results of the light-emitting characteristics when a DC voltage was applied to the produced organic EL device.

<Comparative Example 1> The hole transporting layer 4 was formed using a coating solution prepared by replacing the high molecular weight compound A with the following TFB (hole transporting polymer) and dissolving it in toluene to 0.6% by weight. An organic EL device was produced in the same manner as in Example 14. [Chemical 60] (TFB) poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4 '-(N- (4-second butylphenyl)) diphenylamine] ( American Dye Source Corporation, Hole Transport Polymer ADS259BE) For this organic EL device, various characteristics were evaluated in the same manner as in Example 14. The results are shown in Table 1.

And evaluation of various properties, the elements lifetime based measurement of emission luminance (initial luminance) of the light emission starts is set 700cd / m ² and the constant current drive, the light emitting luminance decay becomes 560cd / m ² (corresponding to an initial luminance of 100 80% at 80%: 80% attenuation).

【Table 1】

As shown in Table 1, the organic EL element of Comparative Example 1 was 6.7 cd / A for the luminous efficiency when a current with a current density of 10 mA / cm ² was passed. In contrast, the organic EL element of Example 14 was 7.9 cd / A. The organic EL element of Example 15 was 8.7 cd / A, the organic EL element of Example 16 was 8.3 cd / A, the organic EL element of Example 17 was 6.8 cd / A, and the organic EL element of Example 18 was 8.7 cd / A. The organic EL element of Example 19 was 9.0 cd / A, the organic EL element of Example 20 was 8.6 cd / A, the organic EL element of Example 21 was 8.8 cd / A, and the organic EL element of Example 22 was 9.2 cd. / A, the organic EL element of Example 23 is 9.6 cd / A, the organic EL element of Example 24 is 8.3 cd / A, and the organic EL element of Example 25 is 10.7 cd / A, all of which are high efficiency. For the element lifetime (80% attenuation), the organic EL element of Comparative Example 1 was 194 hours, while the organic EL element of Example 14 was 205 hours, the organic EL element of Example 15 was 531 hours, and the organic EL element of Example 16 was The EL element is 276 hours, the organic EL element of Example 17 is 231 hours, the organic EL element of Example 18 is 251 hours, the organic EL element of Example 19 is 478 hours, the organic EL element of Example 20 is 312 hours, The organic EL element of Example 21 is 264 hours, the organic EL element of Example 22 is 380 hours, the organic EL element of Example 23 is 260 hours, and the organic EL element of Example 24 is 210 hours, which are long lifetimes.

As described above, it can be seen that an organic EL device including an organic layer formed using the high molecular weight compound of the present invention can achieve an organic EL device with higher luminous efficiency and longer life than a conventional organic EL device.

<Example 26> Measurement and Evaluation of Residual Film Rate; A thin film was formed on a glass substrate by a spin coating method using a solution in which the high molecular weight compound A synthesized in Example 1 was dissolved in toluene to 0.6% by weight. The obtained film was transferred into a glove box replaced with dry nitrogen, and baked on a hot plate at 200 ° C for 1 hour. After the baked film was cooled to room temperature, the absorption intensity of light having a wavelength of 300 to 700 nm was measured using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). Moreover, the film whose absorption strength was measured was rinsed with toluene using a spin coater at 2000 rpm for 15 seconds. The absorption intensity of the rinsed film was measured using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). From the absorption intensity before and after the rinsing measured as described above, the residual film rate was calculated according to the following formula. The results are shown in Table 2. Residual film rate (%) = (α / β) × 100 In the formula, α is the absorption intensity (peak top) after washing, and β is the absorption intensity (peak top) before washing.

<Example 27> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound B synthesized in Example 2, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Example 28> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound C synthesized in Example 3, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Example 29> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound D synthesized in Example 4, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Example 30> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound E synthesized in Example 5, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Example 31> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound F synthesized in Example 6, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Example 32> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound G synthesized in Example 7, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Example 33> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound H synthesized in Example 8, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Example 34> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound I synthesized in Example 9, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Example 35> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound J synthesized in Example 10, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Example 36> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound K synthesized in Example 11, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Example 37> Except that the high-molecular-weight compound A was replaced with the high-molecular-weight compound L synthesized in Example 12, the same procedure as in Example 26 was performed to calculate the residual film ratio. The results are shown in Table 2.

<Comparative Example 2> Except that the high molecular weight compound A was changed to TFB used in Comparative Example 1, the same procedure as in Example 26 was performed to calculate the residual film rate. The results are shown in Table 2.

【Table 2】

As shown in Table 2, the baking of the high molecular weight compounds A to L at 200 ° C / 60 minutes all showed a high residual film rate of 90% or more. The high molecular weight compounds of the present invention are considered to have high hardening properties (thermal crosslinkability). . [Industrial availability]

The high molecular weight compound of the present invention has a high hole transporting ability, excellent electron blocking ability, and good thermal crosslinkability. Therefore, it is an excellent compound for coating organic EL devices. By using the compound to produce a coated organic EL element, high luminous efficiency and power efficiency can be obtained, and durability can be improved. For example, it can be used for household electric products and lighting.

1‧‧‧ glass substrate

2‧‧‧ transparent anode

3‧‧‧ Hole injection layer

4‧‧‧ Hole transporting layer

5‧‧‧ luminescent layer

6‧‧‧ electron transport layer

7‧‧‧ cathode

FIG. 1 is a view showing the chemical structures of the ideal structural units 1 to 3 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 2 is a diagram showing chemical structures of ideal structural units 4 to 6 as substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 3 is a view showing chemical structures of ideal structural units 7 to 9 as substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 4 is a view showing the chemical structures of the ideal structural units 10 to 12 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 5 is a diagram showing the chemical structures of the ideal structural units 13 to 15 as the substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 6 is a view showing chemical structures of ideal structural units 16 to 18 as substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 7 is a diagram showing the chemical structures of the ideal structural units 19 to 21 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 8 is a diagram showing the chemical structures of the ideal structural units 22 to 24 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 9 is a view showing a chemical structure of ideal structural units 25 to 27 as substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 10 is a view showing a chemical structure of an ideal structural unit 28 to 30 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 11 is a view showing the chemical structures of the ideal structural units 31 to 33 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 12 is a diagram showing the chemical structures of the ideal structural units 34 to 36 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 13 is a diagram showing the chemical structures of the ideal structural units 37 to 39 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 14 is a view showing a chemical structure of an ideal structural unit 40 to 42 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 15 is a diagram showing the chemical structures of the ideal structural units 43 to 45 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 16 is a view showing a chemical structure of ideal structural units 46 to 48 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 17 is a view showing a chemical structure of an ideal structural unit 49 to 51 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 18 is a diagram showing the chemical structures of ideal structural units 52 to 54 as the substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 19 is a view showing a chemical structure of an ideal structural unit 55 to 57 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 20 is a diagram showing the chemical structure of ideal structural units 58 to 60 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 21 is a diagram showing chemical structures of ideal structural units 61 to 63 as substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 22 is a view showing a chemical structure of an ideal structural unit 64 to 66 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 23 is a diagram showing the chemical structures of the ideal structural units 67 to 69 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 24 is a view showing a chemical structure of an ideal structural unit 70 to 72 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 25 is a view showing a chemical structure of an ideal structural unit 73 to 75 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 26 is a view showing a chemical structure of an ideal structural unit 76 to 78 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 27 is a view showing a chemical structure of an ideal structural unit 79 to 81 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 28 is a view showing the chemical structures of the ideal structural units 82 to 84 of the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 29 is a diagram showing chemical structures of ideal structural units 85 to 87 as substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 30 is a view showing a chemical structure of an ideal structural unit 88 to 90 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 31 is a diagram showing the chemical structures of the ideal structural units 91 to 93 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 32 is a view showing a chemical structure of an ideal structural unit 94 to 96 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 33 is a diagram showing the chemical structures of the ideal structural units 97 to 99 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 34 is a view showing the chemical structure of an ideal structural unit 100 to 102 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 35 is a diagram showing the chemical structures of the ideal structural units 103 to 105 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 36 is a diagram showing the chemical structures of ideal structural units 106 to 108 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 37 is a diagram showing the chemical structure of an ideal structural unit 109 to 111 as a substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 38 is a diagram showing the chemical structures of the ideal structural units 112 to 114 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 39 is a diagram showing the chemical structures of the ideal structural units 115 to 117 of the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 40 is a diagram showing the chemical structures of the ideal structural units 118 to 120 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 41 is a diagram showing chemical structures of ideal structural units 121 to 123 as substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 42 is a diagram showing chemical structures of ideal structural units 124 to 126 as substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 43 is a diagram showing the chemical structures of ideal structural units 127 to 129 as the substituted triarylamine structural units possessed by the high molecular weight compound of the present invention. FIG. 44 is a view showing the chemical structures of the ideal structural units 130 to 132 of the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 45 is a diagram showing the chemical structure of the ideal structural units 133 to 135 as the substituted triarylamine structural unit possessed by the high molecular weight compound of the present invention. FIG. 46 is a diagram showing the chemical structures of the structural units (2a) to (2f) introduced for better solubility in organic solvents. FIG. 47 is a diagram showing the chemical structures of the structural units (2g) to (2l) introduced for better solubility in organic solvents. FIG. 48 is a diagram showing the chemical structures of the structural units (2m) to (2q) introduced for better solubility in organic solvents. FIG. 49 is a diagram showing the chemical structures of the structural units (2r) to (2v) introduced for better solubility in an organic solvent. FIG. 50 is a diagram showing the chemical structures of the structural units (2w) to (2x) introduced for better solubility in organic solvents. FIG. 51 is a diagram showing the chemical structures of structural units (3a) to (3e) introduced for better thermal crosslinkability. FIG. 52 is a diagram showing chemical structures of structural units (3f) to (3j) introduced for better thermal crosslinkability. FIG. 53 is a diagram showing chemical structures of structural units (3k) to (3n) introduced for better thermal crosslinkability. FIG. 54 is a diagram showing chemical structures of structural units (3o) to (3r) introduced for better thermal crosslinkability. FIG. 55 is a diagram showing chemical structures of structural units (3s) to (3v) introduced for better thermal crosslinkability. FIG. 56 is a diagram showing chemical structures of structural units (3w) and (3y) introduced for better thermal crosslinkability. FIG. 57 is a diagram showing an example of a layer structure possessed by the organic element of the present invention. FIG. 58 shows a ¹ H-NMR chart of the high molecular weight compound (Compound A) of the present invention synthesized in Example 1. FIG. FIG. 59 shows a ¹ H-NMR chart of the high molecular weight compound (Compound B) of the present invention synthesized in Example 2. FIG. FIG. 60 shows a ¹ H-NMR chart of the high molecular weight compound (Compound C) of the present invention synthesized in Example 3. FIG. 61 shows a ¹ H-NMR chart of the high molecular weight compound (Compound D) of the present invention synthesized in Example 4. FIG. FIG. 62 shows a ¹ H-NMR chart of the high molecular weight compound (Compound E) of the present invention synthesized in Example 5. FIG. FIG. 63 shows a ¹ H-NMR chart of the high molecular weight compound (Compound F) of the present invention synthesized in Example 6. FIG. 64 shows a ¹ H-NMR chart of the high molecular weight compound (Compound G) of the present invention synthesized in Example 7. FIG. 65 shows a ¹ H-NMR chart of the high molecular weight compound (compound H) of the present invention synthesized in Example 8. FIG. FIG. 66 shows a ¹ H-NMR chart of the high molecular weight compound (Compound I) of the present invention synthesized in Example 9. FIG. FIG. 67 shows a ¹ H-NMR chart of the high molecular weight compound (Compound J) of the present invention synthesized in Example 10. FIG. FIG. 68 shows a ¹ H-NMR chart of the high molecular weight compound (Compound K) of the present invention synthesized in Example 11. FIG. FIG. 69 shows a ¹ H-NMR chart of the high molecular weight compound (compound L) of the present invention synthesized in Example 12. FIG.

Claims (20)

A high molecular weight compound containing a substituted triarylamine structural unit represented by the following general formula (1); In the formula, Ar ¹ and Ar ^{2 are} each a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group, and R ¹ and R ^{2 are} each a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, or a carbon atom. Alkyl groups of 1 to 8, cycloalkyls of 5 to 10 carbons, alkenyls of 2 to 6 carbons, alkoxys of 1 to 6 carbons, or cycloalkoxys of 5 to 10 carbons, X , Y, and Z are provided that at least one of them is an aryl group or a heteroaryl group, and is an aryl group, a heteroaryl group, or the same group as the group represented by R ¹ and R ² . For example, the high molecular weight compound of the first patent application range is a polymer containing the structural unit as a repeating unit. In terms of polystyrene, it has a weight average molecular weight of 10,000 or more and less than 1,000,000. For example, the high-molecular-weight compound according to item 1 of the application, wherein X and Y in the general formula (1) are an aryl group or a heteroaryl group. For example, the high-molecular-weight compound in the third item of the patent application, wherein the aryl group and the heteroaryl group have no substituent. For example, the high molecular weight compound in the fourth item of the patent application, wherein in the general formula (1), X and Y are phenyl, biphenyl, bitriphenyl, naphthyl, phenanthryl, fluorenyl, naphthylphenyl Or triphenylene. For example, the high-molecular-weight compound according to item 1 of the patent application range, wherein, in the general formula (1), R ¹ , R ² and Z are a hydrogen atom or a deuterium atom. For example, the high-molecular-weight compound according to item 1 of the patent application range, wherein, in the general formula (1), X and Z are an aryl group or a heteroaryl group. For example, the high-molecular-weight compound according to item 7 of the application, wherein the aryl group and the heteroaryl group have no substituent. For example, in the high molecular weight compound of the eighth patent application, in the general formula (1), X and Z are phenyl, biphenyl, bitriphenyl, naphthyl, phenanthryl, fluorenyl, naphthylphenyl Or triphenylene. For example, the high-molecular-weight compound according to item 1 of the application, wherein in the general formula (1), R ¹ , R ² and Y are a hydrogen atom or a deuterium atom. For example, the high-molecular-weight compound according to the first patent application range, wherein, in the general formula (1), X, Y, and Z are all aryl or heteroaryl. For example, the high molecular weight compound in the scope of application for item 11 wherein the aryl or heteroaryl group has no substituent. For example, the high molecular weight compound in the patent application No. 12 wherein X, Y and Z in the general formula (1) are all phenyl, biphenyl, bitriphenyl, naphthyl, phenanthryl, fluorenyl, naphthalene Phenyl or triphenylene. For example, the high-molecular-weight compound according to item 1 of the patent application range, wherein, in the general formula (1), R ¹ and R ² are a hydrogen atom or a deuterium atom. For example, the high-molecular-weight compound of the first patent application scope has a unit having at least one aromatic hydrocarbon ring or a structural unit having a triarylamine skeleton separately from the unit represented by the general formula (1). An organic electroluminescence element has a pair of electrodes and at least one organic layer sandwiched between the electrodes, and is characterized in that the organic layer contains a high-molecular-weight compound as described in item 1 of the scope of patent application. For example, the organic electroluminescence element in the 16th aspect of the application for a patent, wherein the organic layer is a hole transporting layer. For example, the organic electroluminescent device according to the 16th aspect of the patent application, wherein the organic layer is an electron blocking layer. For example, the organic electroluminescence device of the 16th aspect of the application for a patent, wherein the organic layer is a hole injection layer. For example, the organic electroluminescence element in the 16th aspect of the patent application, wherein the organic layer is a light emitting layer.